Location‐Specific Microenvironment Modulation Around Single‐Atom Metal Sites in Metal–Organic Frameworks for Boosting Catalysis

Abstract Despite coordination environment of catalytic metal sites has been recognized to be of great importance in single‐atom catalysts (SACs), a significant challenge remains in the understanding how the location‐specific microenvironment in the higher coordination sphere influences their catalysis. Herein, a series of Cu‐based SACs, namely Cu 1 /UiO‐66‐X (X=‐NO 2 , ‐H, and ‐NH 2 ), are successfully constructed by anchoring single Cu atoms onto the Zr‐oxo clusters of metal–organic frameworks (MOFs), i.e., UiO‐66‐X. The ‐X functional groups dangling on the MOF linkers could be regarded as location‐specific remote microenvironment to regulate electronic properties of the single Cu atoms. Remarkably, they exhibit significant differences in the catalysis toward the hydroboration of alkynes. The activity follows the order of Cu 1 /UiO‐66‐NO 2 > Cu 1 /UiO‐66 > Cu 1 /UiO‐66‐NH 2 under identical reaction conditions, where Cu 1 /UiO‐66‐NO 2 showcases the phenylacetylene conversion of 92 %, ~3.5 times higher efficiency than that of Cu 1 /UiO‐66‐NH 2 . Experimental and calculation results jointly support that the Cu electronic structure is modulated by the location‐specific microenvironment, thereby regulating the product desorption and promoting the catalysis.